Ethyl trifluoroacetate → HCID 22185798, compound

HRID 1795198Notes

Reaction equation

HRID 1795198 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][CH:3]=1.[C:12]([C:15]1[CH:20]=[CH:19][C:18](B(O)O)=[CH:17][CH:16]=1)(=[O:14])[CH3:13].C([O-])([O-])=O.[K+].[K+].[F:30][C:31]([F:38])([F:37])[C:32](OCC)=[O:33].[H-].[Na+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].O.C(Cl)Cl.CC([O-])=O.CC([O-])=O.[Pd+2]>[F:30][C:31]([F:38])([F:37])[C:32](=[O:33])[CH2:13][C:12]([C:15]1[CH:20]=[CH:19][C:18]([C:2]2[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][CH:3]=2)=[CH:17][CH:16]=1)=[O:14]

Participants

10

Reactant 5

HCID 9794Ethyl trifluoroacetateHCID 11430Potassium CarbonateHCID 24758Sodium hydrideHCID 67872Benzene, 1-bromo-4-(trifluoromethyl)-HCID 37021224-Acetylphenylboronic acid

Product 1

HCID 22185798HCID 22185798, compoundYield 132.5%

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
70 °C

Procedure

synthesis. Step a. The preparation of 4-(4-trifluoromethylphenyl)acetophenone was carried out as follows. To the mixture of 4-bromobenzotrifluoride (1.0 g, 4.4 mmol) and 4-acetylphenylboronic acid (0.739 g, 4.4 mmol), Pd(OAc)2 (1.97 mg), K2CO3 (1.54 g), Bu4NBr (1.43 g) and H2O (7 mL) were added, The mixture was stirred under argon for 30 min, warmed to 70° C., and kept stirring for 1 hr. The solution was cooled to room temperature, diluted with water, extracted with ethyl acetate. The intermediate was purified by Silica gel chromatography with yield of 86%. Step b. To a cooled solution of ethyl trifluoroacetate (1.0 g, 7.04 mmol) in CH2Cl2, NaH (338 mg, 14.1 mmol) was added, stirred for 15 min., and then a solution of 4-(4-trifluoromethylphenyl)acetophenone (1.86 g, 7.04 mmol) in CH2Cl2 was added. The mixture was stirred at room temperature for 6 hrs, Silica gel chromatography afforded the 4,4,4-trifluoro-1-(4-(4-trifluoromethylphenyl)phenyl)butane-1,3-dione (2.1 g, 83% yield). Step c. (4-Sulfamoylphenyl) hydrazine hydrochloride (200 mg, 0.89 mmol) was added to a stirred solution of the above dione (320 mg, 0.89 mmol) in 20 mL of ethyl acetate, The mixture was headed to reflux and stirred for 24 hr. After cooling to room temperature, the reaction mixture was concentrated in vacuo. The residue was dissolved in ethyl acetate, washed with water and brine. The product was purified by chromatography to give the title compound (290 mg, 71% yield).

Workup

  1. customsynthesis
  2. additionwere added
  3. stirringkept stirring for 1 hr
  4. temperatureThe solution was cooled to room temperature
  5. extractionextracted with ethyl acetate
  6. customThe intermediate was purified by Silica gel chromatography with yield of 86%
  7. stirringstirred for 15 min.
  8. stirringThe mixture was stirred at room temperature for 6 hrs

Sources & evidence

ORD record
ord-c86d860b98c74cd59f3e5869aab7fd31
Source dataset
uspto-grants-2006_04
Patent number
US07026346B2

Reaction notes

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